US4544453A - Stripping of unreacted glycol ethers and acids from an esterification reaction mixture - Google Patents

Stripping of unreacted glycol ethers and acids from an esterification reaction mixture Download PDF

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US4544453A
US4544453A US06/615,393 US61539384A US4544453A US 4544453 A US4544453 A US 4544453A US 61539384 A US61539384 A US 61539384A US 4544453 A US4544453 A US 4544453A
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unreacted
ether
acid
water
solvent
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Vijai P. Gupta
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Lyondell Chemical Technology LP
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Atlantic Richfield Co
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Priority to CA000482480A priority patent/CA1217448A/en
Priority to JP60116343A priority patent/JPS611641A/ja
Priority to EP85303754A priority patent/EP0163522B1/en
Priority to DE19853564803 priority patent/DE3564803D1/de
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Definitions

  • a monocarboxylic or halogenated monocarboxylic acid having from 1 to 10 carbon atoms with an alkylene glycol monoalkyl ether having the formulae R(OCH 2 CHR') n OH and ##STR1## wherein R is a straight or branched chain alkyl group containing from 1 to 10 carbon atoms, R' is hydrogen or a methyl group and n is an integer of from 1 to 3, in the presence of an acid catalyst and a water-azeotroping solvent which forms a binary minimum-boiling azeotrope with water within the reaction temperature range.
  • Water is removed via a distillation column during the reaction by azeotropic distillation with the water-azeotroping solvent and the solvent phase and water phase are separated and the solvent phase along with a portion of the water phase returned and refluxed to the overhead section of the distillation column.
  • the desired monocarboxylic acid ester is then recovered and may be used as solvents for inks and coating polymers and in cleansers.
  • the acid is reacted with an alkylene glycol monoalkyl ether generally in the presence of an inert azeotroping solvent such as toluene with an acid catalyst such as paratoluenesulfonic acid.
  • an inert azeotroping solvent such as toluene
  • an acid catalyst such as paratoluenesulfonic acid.
  • the rate of further reaction becomes so low because of equilibrium limitations that the reaction is terminated and the unreacted alkylene glycol monoalkyl ether and monocarboxylic acid, which would be present at between about 10% to 2.5% each in the monocarboxylic acid ester product, are stripped out by distillation.
  • Lower conversion mixtures e.g. 50% ester, which would, for example, contain 25% monocarboxylic acid and 25% glycol ether, may also be concentrated to an 80-95% ester containing range by a straight distillation prior to employment of the water injection method of the present invention.
  • the present invention relates to the stripping step and provides a novel method of injecting water into the distillate to provide for a separation and refluxing of an azeotropic solvent to the distillation column during stripping to improve the separation of the unreacted ether and acid reactants.
  • This invention relates to a novel method of stripping by azeotropic distillation unreacted alkylene glycol monoalkyl ethers and unreacted monocarboxylic or halogenated monocarboxylic acids which are contained in the reaction mixture resulting from an acid catalyzed esterification reaction for the preparation of an alkylene glycol monoalkyl ether ester such as propylene glycol monomethyl ether acetate.
  • FIGURE is a schematic diagram of a specific flow system which can be used to carry out the process of this invention.
  • unreacted monocarboxylic acids and unreacted alkylene glycol monoalkyl ethers which have been utilized in the preparation of an alkylene glycol monoalkyl ether ester and remain in admixture therewith are stripped by azeotropic distillation from the esterification reaction mixture using inert azeotroping solvents while injecting water into the vaporous distillate in order to provide for a separation and refluxing of the azeotropic solvent to the distillation column during the stripping to improve the removal of the monocarboxylic acid and glycol ether and thus provide higher purity ester product.
  • the stripping of the unreacted acids and ethers may be carried out in the same equipment which was utilized for the catalyzed esterification reaction or other suitable distillation equipment which is equipped with a means for regulating temperature and a means, such as a distillation column, means for the injection of water into the distillate vapor, a condenser and a phase separator or decanter, for removal of the solvent-acid-ether azeotrope and a means for returning the azeotroping solvent to the distillation column.
  • a means such as a distillation column, means for the injection of water into the distillate vapor, a condenser and a phase separator or decanter, for removal of the solvent-acid-ether azeotrope and a means for returning the azeotroping solvent to the distillation column.
  • a general procedure for carrying out the stripping method is to heat the distillation pot or still containing the alkylene glycol monoalkyl ether ester product, unreacted monocarboxylic acid and alkylene glycol monoalkyl ether, a small amount of esterification catalyst and an inert azeotroping solvent to the desired temperature for an appropriate time while azeotroping off the unreacted acid and ether and injecting water into the distillate vapor which is condensed and sent to a phase separator.
  • the azeotroping solvent is returned as reflux and the water containing the unreacted acid and ether is removed for further processing.
  • the water which is injected into the distillate to extract the monocarboxylic acid and glycol ether may be from any source, i.e., fresh water or water which may be reclaimed from the glycol ether-carboxylic acid reaction to prepare the ester as described in the above mentioned Gupta application Ser. No. 476,305.
  • the unreacted alkylene glycol monoalkyl ethers which are stripped, according to the present method, from the esterification reaction mixture conform to the general formula R(OCH 2 CHR') n OH and the isomer ##STR2## may be prepared for example by the process disclosed in U.S. Pat. Nos. 2,816,932 and 4,299,997.
  • alkylene glycol monoalkyl ethers within the above noted formula and suitable for use in this invention include, for example, ethylene glycol and diethylene glycol monomethyl, -ethyl, -propyl, -isopropyl, -butyl, -tertiary-butyl, -isobutyl, -amyl, -hexyl, -octyl, -decyl, etc., ethers, propylene glycol, dipropylene glycol and tripropylene glycol mono-methyl, -ethyl, -propyl, -isopropyl, -butyl, -amyl, -octyl, -decyl, etc., ethers.
  • the monocarboxylic acid which are employed as reactants in the esterification reaction and are removed according to the present invention include monocarboxylic and halogenated monocarboxylic acids having from 1 to 10 carbon atoms.
  • Representative monocarboxylic acids include for example, formic, acetic, propionic, n-butyric, isobutyric, caproic, trimethylacetic, chloroacetic, bromoacetic, chloroproponic, etc., acids.
  • the inert azeotroping solvents for use in the process of this invention include those solvents forming a binary minimum-boiling azeotrope with the monocarboxylic acids and glycol ethers at a distillation temperature range of from about 50° C. to 150° C. at atmospheric or subatmospheric pressure.
  • azeotroping solvents include, for example, aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene, bromobenzene, alkanes and cycloalkanes such as n-pentane, trimethylpentane, isopentane, n-hexane, n-heptane, nonane, 3,4-dimethylhexane, 3-ethylhexane, cyclohexane, methyl cyclohexane, cyclopentane, cyclooctane, halogenated aliphatic compounds such as chloroform, carbon tetrachloride, 1,2-dichloroethane, trichloroethane, etc., as well as diethylketone. Toluene is the preferred solvent.
  • the solvent employed in the esterification reaction will generally also be used to strip the unreacted acid and ether according to the present invention
  • the still or pot temperature for the stripping method of the present invention may range between about 50° C. and 150° C. and is preferably between 95° C. and 120° C. Still or pot temperatures will of course be based on the azeotroping solvent and pressure, if any, employed.
  • the glycol ether and acid are preferably stripped under vacuum. Pressures of from about 20 mm Hg up to about 760 mm Hg and preferably from 200 mm Hg to 500 mm Hg may be employed.
  • the inert azeotroping solvent improves the separation of the monocarboxylic acid and glycol ether from the glycol ether ester, if used alone it does not phase separate and would therefore be removed from the system with the condensed distillate since the solvent could not be refluxed or recycled. In the circumstance, a continuous make up of solvent resulting in a large volume inventory of solvent would be necessary.
  • the present invention involving water injection solves this problem and further reduces product glycol ether ester losses.
  • the glycol ether and monocarboxylic acid are miscible with water and can be removed from the solvent phase containing same by extraction with the water injected into the distillate.
  • Any glycol ether ester product which may be carried over with the distillate, has limited solubility in water and cannot be effectively removed from the solvent phase by water extraction and is refluxed to the distillation column.
  • the method of the present invention uses azeotroping solvent to improve the separation of the unreacted glycol ether and carboxylic acid and utilizes water to extract out these unreacted components, allowing the azeotroping solvent to be returned as reflux which eliminates any need for a continuous makeup of solvent.
  • the water injection rate into the distillate prior to condensation and removal will be at least 5% by weight of the distillate vapor and is preferably injected at a rate of between about 50% to 300% by weight of the distillate vapor.
  • Water could be injected into the top of the distillation column but is preferably injected into the distillation column vapor line, i.e. upstream of the consenser (as shown in the drawing) to avoid any increase in heat load on the distillation column heating system.
  • the final esterification reaction product mixture may vary in the amount of ester product, unreacted acid and ether reactants, solvent and water content contained therein.
  • a reaction product mixture, after the esterification reaction is about 87% alkylene glycol monoalkyl ether ester, 5% alkylene glycol monoalkyl ether, 5% monocarboxylic acid, 2 to 5% solvent, 0.5% acid catalyst such as para-toluene sulfonic acid and a trace of water.
  • an azeotroping solvent is fed via line 1 to distillation still 2 which contains a reaction product mixture resulting from the preparation, in the same process equipment, of a monocarboxylic acid ester of an alkylene glycol monoalkyl ether such as for example, propylene glycol monomethyl ether acetate by the acid catalyzed esterification of acetic acid with propylene glycol monomethyl ether.
  • a reaction product mixture which has been prepared in a separate reactor section may also be fed to the distillation still via line 1 along with the azeotroping solvent.
  • distillation still is then heated to distillation temperatures by heating coils 3 within the still or by recirculation of the reaction mixture through line 4 via pump 6 to reboiler 5 and through line 7 back into the distillation still.
  • Azeotroping solvent, unreacted glycol ether and monocarboxylic acid as well as small amounts of ester product pass into distillation column 8 which is maintained under vacuuum.
  • a predominantly ether and acid solvent azeotrope is taken off the top of the distillation 8 via line 9 to condenser 10. Water is injected into line 9 upstream of condenser 10 to extract the unreacted ether and acid.
  • the condenser water with the ether and acid and the solvent are then fed to phase separator 12.
  • the azeotroping solvent and water-ether-acid mixture are separated in phase separator 12.
  • the azeotroping solvent and water-ether-acid mixture are separated in phase separator 12.
  • the solvent phase is then removed and refluxed to the distillation column 8 via pump 13 and line 14 while the water-ether-acid phase is removed via pump 15 through line 16 for recovery or recycle of the ether and acid.
  • the method of the present invention will be directed principally to the preparation of the acetic acid ester of propylene glycol monomethyl ether and dipropylene glycol monomethyl ether it is not intended that the method be limited to such ester preparation and those skilled in the art will recognize that the present method is broadly applicable to the preparation of other esters such as propylene glycol monobutyl acetate, dipropylene monooctyl butyrate, ethylene glycol monoethyl formate, etc., using the appropriate glycol ether and monocarboxylic acid.
  • esters such as propylene glycol monobutyl acetate, dipropylene monooctyl butyrate, ethylene glycol monoethyl formate, etc.
  • a straight batch distillation employing a 20 tray Oldershaw column at a reflux ratio of 10/1 at atmospheric pressure with a pot temperature of 140°-146° C. and an overhead temperature of 115°-140° C. was carried out on a reaction mixture resulting from an acid catalyzed esterification of propylene glycol monomethyl ether (PM) and acetic acid to produce propylene glycol monomethyl acetate (PMA).
  • the reaction mixture contained on a percent by weight basis 97.2% propylene glycol monomethyl ether acetate, 2.0% unreacted acetic acid, 0.1% unreacted propylene glycol monomethyl ether and 0.7% p-toluene sulfonic acid catalyst.
  • the distillation was carried out for 1 hour and a 14% overhead cut taken. The results were as follows:
  • Example 2 The procedure of Example 1 was repeated. The same equipment was employed except that toluene was continuously added to the still pot at a reflux ratio of 10/1 at atmospheric pressure, an overhead temperature of 104° C.-105° C. and a bottoms temperature of 140° C.
  • the still pot contained on a % by weight basis, 97.5% propylene glycol monomethyl ether acetate (PMA), 1.8% acetic acid, 0.6% p-toluenesulfonic acid and a trace of propylene glycol monomethyl ether.
  • PMA propylene glycol monomethyl ether acetate
  • the distillation was carried out for 4 hours. The results were as follows:
  • the acetic acid content of the product bottoms was reduced to less than 0.1% with a solvent feed of 22% of the reactor charge.
  • Example 1 The procedure of Example 1 was repeated except that 7% by weight toluene was added to the pot and water was injected into the vaporous distillate at a rate of 1 cc and 2 cc/min. The distillate was phase separated with Dean Stark apparatus. The toluene solvent phase was refluxed to the column and the water phase containing unreacted acetic acid and a trace of propylene glycol monomethyl ether was removed. No propylene glycol monomethyl ether acetate product was in the water phase.
  • Example 3 the distillation pot charge contained on a percent by weight basis, 97.7% PMA, 1.56% acetic acid, 0.7% p-toluenesulfonic acid and a trace amount of propylene glycol monomethyl ether.
  • the results of Example 3 (water injection at 1 cc/minute were as follows:
  • Example 3 and 4 The procedure of Example 3 and 4 was repeated with the injection of water into the overhead vaporous distillate and a solvent reflux. A 30 tray Oldershaw was employed using Dean Stark Apparatus to phase separate the toluene solvent and water.
  • the water which was injected to extract the acetic acid and glycol ether from the distillate was recycled water and contained 6 weight percent acetic acid and 12 weight percent propylene glycol monomethyl ether.
  • the charge to the distillation pot which resulted from an acid catalyzed esterification reaction contained 84% by wt. propylene glycol monomethyl ether acetate product (PMA), 5.0% by wt. unreacted acetic acid, 6.0% by wt.
  • PMA propylene glycol monomethyl ether acetate product

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US06/615,393 1983-03-17 1984-05-30 Stripping of unreacted glycol ethers and acids from an esterification reaction mixture Expired - Fee Related US4544453A (en)

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US06/615,393 US4544453A (en) 1983-03-17 1984-05-30 Stripping of unreacted glycol ethers and acids from an esterification reaction mixture
CA000482480A CA1217448A (en) 1984-05-30 1985-05-27 Stripping of unreacted glycol ethers and acids from an esterification reaction mixture
EP85303754A EP0163522B1 (en) 1984-05-30 1985-05-29 Stripping of unreacted glycol ethers and acids from an esterification reaction mixture
DE19853564803 DE3564803D1 (enrdf_load_stackoverflow) 1984-05-30 1985-05-29
JP60116343A JPS611641A (ja) 1984-05-30 1985-05-29 エステル化反応混合物から末反応グリコールエーテル及び酸を除去する方法

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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4675082A (en) * 1986-09-22 1987-06-23 Atlantic Richfield Company Recovery of propylene glycol mono t-butoxy ether
US5202463A (en) * 1991-09-10 1993-04-13 Arco Chemical Technology, L.P. Process for the preparation of a glycol ether ester
US5208367A (en) * 1991-12-17 1993-05-04 Exxon Chemical Patents Inc. Process for recovery of vinyl acetate
US5239111A (en) * 1992-10-14 1993-08-24 Shiny Chemical Industrial Co., Ltd. Propylene glycol monomethyl ether propionate compound and the process for the preparation thereof
US5321152A (en) * 1992-10-14 1994-06-14 Shiny Chemical Industrial Co., Ltd. Propylene glycol monomethyl ether propionate compounds and the process for the preparation thereof
EP0711747A1 (en) 1994-11-10 1996-05-15 Union Carbide Chemicals & Plastics Technology Corporation Esterification process
US6610638B1 (en) * 1999-03-31 2003-08-26 Daicel Chemical Industries, Ltd. High purity 1,3-propanediol derivative solvent, process for producing the same, and use thereof
US20050156609A1 (en) * 1999-07-26 2005-07-21 Paul Pfaff Voltage testing and measurement
US20050231733A1 (en) * 2002-05-03 2005-10-20 Paul Pfaff Non-destructive testing system
US20060244974A1 (en) * 2001-12-06 2006-11-02 Attofemto, Inc. Non-destructive testing system
US20090110838A1 (en) * 2004-09-02 2009-04-30 Hitachi Chemical Co., Ltd Composition for forming silica-based film, method of forming silica-based film, and electronic component provided with silica-based film
KR101134659B1 (ko) 2010-09-06 2012-04-09 이수화학 주식회사 프로필렌 글리콜 모노메틸 에테르 아세테이트의 제조방법
JP2015030700A (ja) * 2013-08-02 2015-02-16 株式会社ダイセル エステル系溶剤の製造方法
WO2018192195A1 (zh) * 2017-04-20 2018-10-25 江苏华伦化工有限公司 一种半导体级丙二醇甲醚醋酸酯的制备方法
CN114192086A (zh) * 2021-12-16 2022-03-18 中建安装集团有限公司 一种隔板反应精馏生产丙二醇单甲醚醋酸酯的装置及工艺
KR102444197B1 (ko) 2022-03-14 2022-09-20 베니트엠 주식회사 Pgme, pgmea, 물의 혼합물로부터 물을 분리하는 방법
CN114409500B (zh) * 2022-01-25 2024-03-15 福建钰融科技有限公司 一种从电子废液中回收丙二醇甲醚和丙二醇单甲醚醋酸酯的方法

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US2423545A (en) * 1944-07-13 1947-07-08 Norda Essential Oil & Chemical Esterification of terpene alcohols
US3374153A (en) * 1966-07-25 1968-03-19 Halcon International Inc Process for recovery of glycidol from alcohol by azeotropic distillation with a hydrocarbon
US3476798A (en) * 1963-05-09 1969-11-04 Wacker Chemie Gmbh Process for separating azeotropic mixtures from esters of aliphatic saturated or unsaturated carboxylic acids and alcohols by azeotropic distillation with a hydrocarbon halide
US3923874A (en) * 1972-06-10 1975-12-02 Basf Ag Continuous production of esters of glycols or their monoethers with lower fatty acids

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US3951756A (en) * 1974-11-08 1976-04-20 Celanese Corporation Purification of alkyl esters

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2423545A (en) * 1944-07-13 1947-07-08 Norda Essential Oil & Chemical Esterification of terpene alcohols
US3476798A (en) * 1963-05-09 1969-11-04 Wacker Chemie Gmbh Process for separating azeotropic mixtures from esters of aliphatic saturated or unsaturated carboxylic acids and alcohols by azeotropic distillation with a hydrocarbon halide
US3374153A (en) * 1966-07-25 1968-03-19 Halcon International Inc Process for recovery of glycidol from alcohol by azeotropic distillation with a hydrocarbon
US3923874A (en) * 1972-06-10 1975-12-02 Basf Ag Continuous production of esters of glycols or their monoethers with lower fatty acids

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4675082A (en) * 1986-09-22 1987-06-23 Atlantic Richfield Company Recovery of propylene glycol mono t-butoxy ether
US5202463A (en) * 1991-09-10 1993-04-13 Arco Chemical Technology, L.P. Process for the preparation of a glycol ether ester
US5208367A (en) * 1991-12-17 1993-05-04 Exxon Chemical Patents Inc. Process for recovery of vinyl acetate
US5239111A (en) * 1992-10-14 1993-08-24 Shiny Chemical Industrial Co., Ltd. Propylene glycol monomethyl ether propionate compound and the process for the preparation thereof
US5321152A (en) * 1992-10-14 1994-06-14 Shiny Chemical Industrial Co., Ltd. Propylene glycol monomethyl ether propionate compounds and the process for the preparation thereof
EP0711747A1 (en) 1994-11-10 1996-05-15 Union Carbide Chemicals & Plastics Technology Corporation Esterification process
US5618973A (en) * 1994-11-10 1997-04-08 Union Carbide Chemicals & Plastics Technology Corporation Esterification process
US6610638B1 (en) * 1999-03-31 2003-08-26 Daicel Chemical Industries, Ltd. High purity 1,3-propanediol derivative solvent, process for producing the same, and use thereof
US20050156609A1 (en) * 1999-07-26 2005-07-21 Paul Pfaff Voltage testing and measurement
US20060244974A1 (en) * 2001-12-06 2006-11-02 Attofemto, Inc. Non-destructive testing system
US20050231733A1 (en) * 2002-05-03 2005-10-20 Paul Pfaff Non-destructive testing system
US20090110838A1 (en) * 2004-09-02 2009-04-30 Hitachi Chemical Co., Ltd Composition for forming silica-based film, method of forming silica-based film, and electronic component provided with silica-based film
US8466229B2 (en) * 2004-09-02 2013-06-18 Hitachi Chemical Co., Ltd. Composition for forming silica-based film, method of forming silica-based film, and electronic component provided with silica-based film
KR101134659B1 (ko) 2010-09-06 2012-04-09 이수화학 주식회사 프로필렌 글리콜 모노메틸 에테르 아세테이트의 제조방법
JP2015030700A (ja) * 2013-08-02 2015-02-16 株式会社ダイセル エステル系溶剤の製造方法
WO2018192195A1 (zh) * 2017-04-20 2018-10-25 江苏华伦化工有限公司 一种半导体级丙二醇甲醚醋酸酯的制备方法
CN114192086A (zh) * 2021-12-16 2022-03-18 中建安装集团有限公司 一种隔板反应精馏生产丙二醇单甲醚醋酸酯的装置及工艺
CN114409500B (zh) * 2022-01-25 2024-03-15 福建钰融科技有限公司 一种从电子废液中回收丙二醇甲醚和丙二醇单甲醚醋酸酯的方法
KR102444197B1 (ko) 2022-03-14 2022-09-20 베니트엠 주식회사 Pgme, pgmea, 물의 혼합물로부터 물을 분리하는 방법
WO2023177133A1 (ko) 2022-03-14 2023-09-21 베니트엠 주식회사 Pgme, pgmea, 물의 혼합물로부터 물을 분리하는 방법

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EP0163522B1 (en) 1988-09-07
EP0163522A3 (en) 1986-03-05
EP0163522A2 (en) 1985-12-04
JPS611641A (ja) 1986-01-07
CA1217448A (en) 1987-02-03
DE3564803D1 (enrdf_load_stackoverflow) 1988-10-13

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